Silver halide photographic elements containing sulfonic acid substituted aroylacetarylide couplers



United States Patent 3,393,040 SILVER HALIDE PHOTOGRAPHIC ELEMENTS CONTAINING SULFONIC ACID SUBSTITUTED AROYLACETARYLIDE COUPLERS Marcel Hendrik Verbrugghe, Wilrijk-Antwerp, Arthur Henri De Cat, Mortsel-Antwerp, and Valre Frans Danckaert, Boechout, Belgium, assignors to Gevaert Photo-Producteu N.V., Mortsel, Belgium, a company of Belgium No Drawing. Filed July 8, 1964, Ser. No. 381,238 Claims priority, application Belgium, July 9, 1963, 42,771, Patent 634,669 8 Claims. (Cl. 96-74) This invention relates to the production of photographic color images, to the color couplers for yellow used therein and to photographic material containing such color couplers.

It is known that for the production of a photographic color image in a light-sensitive silver halide emulsion layer, the exposed silver halide is developed to a silver image with an aromatic primary amino compound in the presence of a color coupler by means of which, by reaction with the oxidized developing substance, a dye-stuff is formed on the areas corresponding with the silver image.

In the substractive three-color photography is mostly used a light-sensitive photographic color material containing a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wherein 'by the use of appropriate color couplers in the color development a cyan, magenta and yellow dyestuff image respectively is formed.

It is known that color couplers have to meet different requirements according to the way wherein the color material is prepared and the object for which it is used.

For producing a usable photographic multilayer color image'containing the color couplers for the different color part images in the differently sensitized silver halide emulsion layers, the color couplers shall be present in diffusionfast form in the hydrophilic silver halide emulsion layer. This can, be realized e.g. by using a color coupler which is sufficiently water-soluble and which is provided with a sufficiently extensive organic radical in order to prevent dilfusion of the color coupler into the hydrophilic silver halide emulsion layer, or by the use of a lipophilic color coupler which dissolved in an organic solvent is dispersed in the silver halide emulsion layer.

For the production of color images, more particularly of positive color images, e.g. on a paper support, it is of importance to dispose of color couplers which on color develpment form dyestufis which are very stable to light, humidity and heat.

Now has been found a class of color couplers for yellow of the ketomethylene type, more especially of the aroylacetarylide type the representatives of which in the color development form with an aromatic primary amino developing substance dyestuffs which possess a very good light-, humidityand heat-stability.

These ketomethylene color couplers of the aroylacetarylide type are characterized by the presence of at least one sulfonic acid group in the aroyl part of the molecule and by the presence of at least one sulfonic acid group in the arylide part of the molecule.

Thus one or more sulfonic acid groups may directly be implanted on the aromatic nucleus of the aroyl group and in the same molecule one or more sulfonic acid groups may directly be implanted on the aromatic nucleus of the arylide group.

Thus, also at least one of the aromatic nuclei of the aroyland of the arylide group can be bound by means of a bivalent radical with an aromatic nucleus substituted by at least one sulfonic acid group.

Examples of color couplers for yellow according to the 3,393,040 Patented July 16, 1968 'ice present invention wherein at least one sulfonic acid group is implanted directly on the aromatic nucleus of the aroyl group and at least one sulfonic acid group directlyon the aromatic nucleus of the arylide group, are represented by the following general formula:

wherein:

R represents a sulfonic acid group or salt form thereof,

R represents a hydrogen atom, a substitutent such as for instance a halogen atom, a sulfonic acid group or a salt form thereof, or a diffusion-fast making group such as e.g. an organic group containing an acyclic aliphatic radical with 5 to 20 carbon atoms such as e.g. a n-hexadecyloxy group,

R represents a sulfonic acid group or a salt form thereof,

R represents a hydrogen atom, a substitutent such as e.g. a halogen atom, a sulfonic acid group or a salt form thereof or a diffusion-fast making group such as e.g. an organic group containing an acyclic aliphatic radical with 5 to 20 carbon atoms such as, e.g. an n-hexadecyloxy group of an n-hexadecylmercapto group, and

R and R together can represent the necessary atoms for forming a sulfonyl substituted aromatic system which may be further substituted.

Examples of color couplers for yellow according to the present invention, wherein at least one sulfonic acid group in the aroyl part of the molecule is bound on an aromatic nucleus which is linked with the aromatic nucleus of the aroyl group by a bivalent radical correspond to the following general formula:

R R4 (II) wherein R R and R have the same significance as given in Formula I,

R, represents a sulfonated aromatic radical either further substituted or not, such as e.g. a sulfonated phenyl group, and

Y represents a bivalent radical such as e.g. a CONH group, a SO NH group or a NHCONH group.

Examples of color couplers for yellow according to the present invention, wherein at least one sulfonic acid group in the arylide part of the molecule is bound on an aromatic nucleus, which is linked by a bivalent radical with the aromatic nucleus of the arylide group, correspond to the following general formula:

wherein R R and R have the same significance as given in Formula I,

R" represents a sulfonated aromatic radical either further substituted or not, such as e.g. a 'sulfonated phenyl group, and

Y, represents a bivalent radical such as e.g. a CONH- group or a -SO NH- group.

Examples of color couplers for yellow according to the present invention, wherein at least one sulfonic acid R R; (IV) wherein:

R and R have the same significance as given in Formula I, Y and R' have the same significance as given in Formula II, and Y and R have the same significance as given in Formula III.

The following reaction scheme illustrates the preparation of color couplers for yellow according to the general Formula I:

C O CHzC O O C2H5+NH2 FSO --OOCH2C ONH FSO SOaF COCHaC ONH NaOH FSO or KOH SOXF COOHaCONH NaOSO SOaONa Herein R or R can contain a diffusion-fast making group.

Hereinafter follows a list of structural formulae of color couplers for yellow according to the present invention:

1. 2)1s Ha moso GOG-H2O ONHU SO ONa K0,s- -o ocmoonnO 3. O (CH2)1sC a 131-943 0 CHzCONH S OaNB S OaNa 4. S( z)raC a Naoas COCHaOONHY SOaNa 5. I S-(CHa)1sCH KOBSAOC o CHsCONH $05K 6. S|( n)rs a Naoso,- -o 0 CHQCONH S03Na 7.

1103s -COCH C0NH--O(CH)15CH xoas oooHzommQ-s-(ommom HaC(GHz)us-0 -oooHio0Nn momma-0G0 o omooun 8 03K 803K The following description illustrates more in detail the above given reaction scheme and the preparation of intermediate products of color couplers for yellow according to the present invention.

1. PREPARATION OF ACID CHLORIDES USED IN SYNTHESIS OF THE B-KETOESTER DERIVATIVES The preparation of these acid chlorides is performed as described in the Belgian patent specification 634,665 filed July 9, 1963.

2. PREPARATION OF THE fl-KETOESTER DERIVATIVES The preparation of the fluorosulfonyl-substituted ketoester derivatives has also been described in said Belgian patent specification.

3. PREPARATION OF FLUOROSULFONYL SUB- STITUTED BENZOYL ACETANILIDES AND AL- KALINE HYDROLYSIS TO SULFONIC ACID DE- RIVATIVES (a) Amino derivatives used (mentioned in Table 1) 2-n-hexadecyloxy-5-fluorosulfonylaniline (Belgian patent specification 590,934)

Z-n-hexadecylthio-5-fluorosulfonylaniline (Belgian patent specification 587,525) 3-fluorosulfonyl-4-n-hexadecyloxyaniline.

First p-n-hexadecyloxynitrobenzene is sulfonated at about 60 C. with sulfuric anhydride in tetrachloroethane. The reaction mixture is left for cooling overnight, the precipitate formed is separated and washed with hexane. The crude sulfonic acid derivative is then converted by neutralization with 2 N sodium hydroxide into the sodium salt. After salting out with aqueous sodium chloride, a white to greyish amorphous product is obtained which is recrystallized from acetonitrile. The 3-sulfo-4-n-hexadecyloxynitrobenzene is obtained in the form of a White crystalline product. Melting point: above 250 C.

This nitrobenzene derivative is converted into the corsponding snlfochloride by treatment with thionylchloride at boiling temperature in the presence of dimethylformamide. After evaporating the excess of thionylchloride and treating with a mixture of benzene and hexane, the 3-chlorosulfonyl-4-hexadecyloxynitrobenzene is obtained as a light-brown to white product. Melting point: 56 C.

Now this compound is allowed to react for 1 hour with potassium fluoride in acetic acid at reflux temperature. After pouring out the reaction mixture into water, separating the precipitate formed and recrystallizing from etha- 1101, the white crystalline 3-f1uorosulfonyl-4-n-hexadecyloxynitrobenzene is obtained. Melting point: 72 C.

This nitro compound is now reduced with iron and hydrochloric acid in ethanol medium at reflux temperature. After the reduction, the reaction mixture is filtered and the amine is separated as hydrochloride. This hydrochloride is suspendcd in methylene chloride and treated with aqueous sodium dicarbonate. Hereby the amine is set free. After separating the organic layer and evaporating off the solvent, the crude product is recrystallized from acetonitrile. White needle-shaped 3-fluorosulfonyl- 4-n-hexadecyloxyaniline crystals are obtained. Melting point: 68 C.

3 fluorosulfonyl 4 n hexadecylmercaptoaniline (Belgian patent specification 587,525).

6 3-fluorosulfonylaniline (British patent specification 308,276).

2-chloro-i-fluorosulfonylaniline (British patent specification 808,276).

(b) Preparation of the corresponding benzoylacetanilides GENERAL METHOD 0.1 mol of amino derivative, 0.1 mol of B-ketoester derivative and 0.2 g. of anhydrous sodium acetate are bought into ccs. of anhydrous xylene. The reaction mixture is heated up to reflux temperature, whereafter a mixture of xylene and the ethanol formed is slowly distilled off until the temperature has risen to 138 C. which lasts about 1 hour.

Thereafter, the remaining xylene is distilled off under reduced pressure. 200 ccs. of hexane are added to the residue. The precipitate formed is filtered off and recrystallized from a suitable solvent.

In Table 1 (col. 3-4) are given the results of con densatious of amines. with 3-ketoesters.

(c) Alkaline hydrolysis to sulfonic acid derivatives of fluorosulfonyl substituted benzoylacetanilides GENERAL METHOD 0.1 mol of sulfonylfluoride is heated with 400 ccs. of acetone to boiling temperature. Whilst stirring, 100 ccs. of 5 N sodium hydroxide (or potassium hydroxide) are slowly added. An exothermic reaction takes place. The reaction mixture is heated for 30 minutes at room temperature, whilst stirring, and afterwards acidified with acetic acid, whereafter it is cooled down to room temperature. The precipitate formed is washed with water and recrystallized from a suitable solvent.

In Table 1 (col. 5 and 6) are given the results of these alkaline hydrolyses. Column 7 refers to the abovementioned structural formulae of color couplers for yellow according to the present invention.

TABLE I Substituted benzoylacetanilide Sulionic acid derivative Number Melting of the Amino derivative used fl-Ketoester derivative used Recrystallizing point Recrystallizing Kind of the structural agent 0.) agent alkali salt formula of the color coupler 2-hexadeeyl0xy-5-fluoro- F018 COCHzCOO C2115 Ethanol -116.... Methanol/water.-. Na-salt 1 sulfonylauiline.

Do Same as above Methanol 87 do K-salt 2 Do F028 COCHCOOC;H5 Isopropanol 103 Isoprtopanol/ Na-salt 3 2-n-hexadecylthio-5- FOzS COCHzCOOCzHa Benzene Ethanol/water do 4 fiuorosulfonylaniliue. K-salt 5 Do Same as above Ethanol 73 Methanol/water-.. Na-salt 6 4-n-hexadecy10xy-5fiuor0- do Isopropauol 142 Isopropanol/ K-salt 7 sulfonylaniline. water.

4-n-hexadeeylthio-5- .do Ethanol 123 Ethanol/water .do 8

fluorosulfonylaniline.

3-fluorosulfonylaniline F028 00 OHzCOOCzI-Is ....do 115 d0 ..d0 9

sa 1oO- achloroe-fluorosulto- Same as above Aceton/methanoL. Isoprofipanol/ do 10 wa er.

nylaniliue.

As specific example of a color coupler for yellow according to the present invention, wherein a sulfonic acid group in the aroyl part of the molecule is bound on an aromatic nucleus which is linked by a bivalent radical with the aromatic nucleus of the aroyl group, is men- 5 tioned a color coupler having the following structural formula:

OCmHaa The following reaction scheme illustrates the synl5 thesis of this color coupler:

-COCHzCOOC2Ht NH:

SOQF

('Z'CIeHaa NoFO-o o CHZC o 0 02115 SOzF H (Ni) (1) NHg COCHzCONH l. SYNTHESIS OF THE STARTING PRODUCTS (a) a- (4'-aminob enzoyl) -2-n-hexadecyloxy-5- fluorosulfonylacetanilide SYNTHESIS STEP 2.

The synthesis of the a-(4'-nitrobenzoyl)-2-n-hexadecyloxy 5 fluorosulfonylacetanilide is analogous to the general method described under 3(b). One starts from 41.5 g. of 2-n-hexadecyloxy-5-fluor0sulfonylaniline (prepared as described in the Belgian patent specification 590,934) and 23.7 g. of 4-nitrobenzoyl acetic acid ethylester, and after recrystallization from benzene the yellow crystalline nitro derivative is obtained. Melting point: 10

4 C SYNTHESIS STEP b This obtained nitro derivative is dissolved in ethylene glycol monomethylether and converted into the corresponding amine by hydrogenation in the presence of Raney-nickel as catalyst. The reduction is carried out under 35 kg./sq.cm hydrogen pressure and at C. After reaction of the calculated amount of hydrogen, the catalyst is filtered off. In the filtrate is formed a precipitate which is separated and recrystallized from dichloroethane. The ot-(4-aminobenzoyl)-2-n-hexadecyloxy-S-fluorosulfonylacetanilide is obtained in the form of a white crystalline product. Melting point: 143 C.

(b) 3-fluorosulfonylbenzoylchloride (Prepared as described in the Belgian patent specification 634,665 filed July 9, 1963.)

2. REACTION OF THE AMINE DERIVATIVE WITH 3-FLUOROSULFONYLBENZOYLCHLORIDE SYNTHESIS STEP 6' The synthesis is analogous to that described in the above-mentioned Belgian patent specification. One starts from 12.12 g. of amine derivative and an equivalent amount of 3-fluorosulfonylbenzoyl chloride. After recrystallization from dichloroethane, a white crystalline product is obtained. Melting point: 186-187 C.

3. ALKALINE HYDROLYSIS TO SULFONIC ACID DERIVATIVE SYNTHESIS STEP d The alkaline hydrolysis of the former sulfonylfluoride derivative is carried out analogously as indicated for the compounds mentioned under the general Formula 1. After recrystallization from a mixture of ethanol and 0 Cm aa s ot]? (111) water, a white crystalline product is finally obtained.

Specific examples of color couplers for yellow according to the present invention, wherein a sulfonic acid 5 group in the arylide part of the molecule is bound on an aromatic nucleus, which is linked with a bivalent radical with the aromatic nucleus of the arylide group, correspond to the following structural formulae:

12. 0 Cw aa mosoO-ooomoozmO-somn l SOgONa 13. 0 10 33 NaOSOU-OOOHzOONHO somn SOzONa The preparation of these color couplers is carried out analogously to that shown in the last mentioned reaction scheme. Only the structure of the amine difiers.

1. SYNTHESIS OF THE AMINE DERIVATIVES (a) 3-(2'-n hexadecyloxy-'-fluorosulfonylfenylaminofulfonyl -aniline 0 CmHaa I First, the Z-n-hexadecyloxy-S-(3-fluorosulfonylphenylaminosulfonyl)-nitrobenzene is prepared in an analogous way as given here-above under (a), starting from 3-flu0rosulfonylaniline and Z-n-hexadecyloxy-S-chlorosulfonylnitrobenzene (Belgian patent specification 590,934). After recrystallization from ethanol, white crystals of the nitro derivative are obtained. Melting point: 112 C.

This nitro derivative is reduced in analogous way as indicated under (a). The 2-n-hexadecyloxy-5-(3-fiu0rosuloz fonylphenylaminosulfonyl)-aniline is obtained as a white NH -S0 NH crystalline product. Melting point: 103 C.

- 2. PREPARATION OF THE SUBSTITUTED 1 BENZOYLACETANILIDES SOBF gt This preparation is carried out in a way analogous to D that of the sbstituted benzylacetanilides, used in the prepaf the l( Y- Y y ration of color couplers according to the general Formula am11'10SI11f0I1Y1)fIIItIObBIIFQIC 1S synthetlled y refluxing I. The results of this synthesis are given in the comparafor minutes atbboihng t6lilf1Pfiiltlll an eguivfillent OI i T bl 2 l, 3 d 4), amount of m-mtro enzene su oc orr 0n 5 3. ALKALINE HYDROLYSIS OF THE FLUORO- decyloxy-S-fiuorosulfonylamlme (Belglan patent specifi- SULFONYL SUBSTITUTED BENZOYLACETANI- cation 590,934). Next, the solvent is distilled off and the LIDES To SULFONIC ACID DERIVATIVES oil residue is treated with methanol. After washing the obtained precipitate with water and recrystallizing from 9 This hydrolysis is likewise carried out in a way analmethanol, the nitrobenzene derivative is obtained asa ogous to that of the fluorosulfonyl substituted benzoylwhite finely granular product. Melting point: 99 C. acetanilides mentioned for the preparation of color cou- This nitro derivative is dissolved in ethanol and conplers according to the general Formula I. verted into the corresponding amine by hydrogenation The results of this alkaline hydrolysis are given in Table in the presence of Raney-nickel as catalyst. The reduc- 2 (cols. 4 and 5).

TABLE 2 Substituted benzoylacetanilide Sulfonie acid derivative (Na-salt) Amine derivative used B-Ketoester used Melting Number of Reerystalllzing point, Recrystallizing the strucagent 0.) agent tural form ula of the color coupler m aa NH,- FOnS- COCHzCOOCzH5 Isopropylether 120 Methanol/water-.." 12

NH, Same as above Isopropanol 120 .do 13 SOzNH SOzF tion is carried out at 105 kg./sq. cm. hydrogen pressure Attention is drawn to the fact that the color couplers and at 80 C. After recrystallization from methanol, the need not necessarily first be separated as sulfonic acid 3-(2-n-hexadecyloxy 5' fluorosulfonylphenylaminosulderivatives before their addition to the silver halide emulfonyl) -ani1ine is obtained as a white crystalline product. sion, but that the sulfonic acid derivatives formed in situ Melting point: 995 C. t E from the sulfonyl fluoride derivatives, by reacting the latter with alkali, can be added as such to the emulsion. (b) gfg gg 'gg i i sgggg For that purpose, preferably 1 mol of sulfonylfiuoride derivative is dissolved in an aqueous solution of 3 mol c9 of sodium hydroxide and the resulting clear solution, after adjusting the pH to agree with the pH of the emulsion NH applied, is added to the silver halide emulsion as a 5 or 10% aqueous solution.

During the preparation of the light-sensitive color material, the non-migratory color couplers for yellow ac- SOzF cording to the above given general formulae are, preferably immediately before coating, homogeneously mixed in dissolved form with the light-sensitive silver halide emulsion. They may also be added to the composition of According to the invention, an exposed silver halide a water-permeable non-light-sensitive layer being in direct emulsion layer is developed with an aromatic primary contact with the light-sensitive silver halide emulsion amino developing substance in the presence of the color layer or they can be incorporated into a non-light-sensicouplers for yellow according to the present invention for tive layer which is separated from the light-sensitive layer 5 obtaining photographic colorimages. by a water-permeable non-light-sensitive layer. The silver All color developing substances capable of forming azohalide emulsion contains the usual colloids such as e.g. methine dyestuifs can be utilized as developers. The color gelatin, polyvinylalcohol, collodion or other suitable natucouplers for yellow according to the present invention ral or synthetic colloids. The photographic emulsion can form on color development with aromatic primary further contain usual ingredients such as hardeners, chemim amines, such as e.g. N-diethyl-p-phenylenediamine, yelcal sensitizers, optical sensitizers, plasticizers, developlow dyestuifs which excel by their favorable light-absorpment activators, stabilizers and wetting agents. tion in the blue-region of the spectrum and their poor The color couplers for yellow according to the above absorption in the other regions. Further, these dyestuffs given general formulae are usually added to a blue-senpossess besides a good heat and humidity stability also sitive silver halide emulsion. According to the most cona good light stability which is shown by comparative tests ventionally applied procedure this silver halide emulsion the description and results follow hereinafter. is coated as first color coupler containing layer of a pho- The resistance to humidity and heat of the dyestuffs tographic multilayer color material. Such photographic to be examined is determined from the decrease in density multilayer color material usually consists successively of of a developed wedge print after having stored, said a support, a red-senistized silver halide emulsion layer wedge print for some determined time (e.g. 7 days) at with color coupler for cyan, a green-sensitized silver halide some determined temperature (e.g. 38 C.) and relative emulsion layer with color coupler for magenta and a bluehumidity (e.g. 95%), while protected from light. sensitive silver halide emulsion layer with color coupler The following table gives a clear showing of-the humfor yellow. The support for this multilayer material can idity and heat stability of dyestulfs formed by the color consist of paper, glass, cellulose nitrate, a cellulose ester development by reaction of the oxidation product of N- such as cellulose triacetate, polyester, polystyrene or any diethyl-p-phenylenediamine formed thereby with a color other synthetic or natural resin. coupler according to the present invention and of the Between the silver halide emulsion layer which conknown color couplers respectively mentioned in the British tains a color coupler for yellow and the green-sensitive patent specifications 808,276 and 783,887.

Maximum Maximum density 7 density after 7 Percent Formula of the color coupler at the days of decrease beginning storing at in max. of the 38 C. at density test 95% relat.

humidity NaOa'S ?C10I'I33 -oo CHzCONH-O 1. 20 1.13 e

| SOaNa 0 w ia NaOSO COCH2CONH,

I SOzNH SO QONZL CmHwO CO CHQOONH SOaNa 1. 20 0.97 20 (color coupler for yellow according to British patent specification 808,276)

GOOH

(color coupler for yellow according to British patent specification 783,887)

silver halide emulsion layer there is usually a yellow filter The resistance to light of the dyestufis formed on delayer which in most cases contains colloidal silver disp Y -PP F Y e and Which persed in gelatin. The sulfonylfiuoride derivatives can be are to be exammed 1S determined from file decrease in density of a developed wedge print on exposing said used as color couplers for yellow 1n the so called droplet Wedge print for some determined time 16 hours) to emulsions (cf. United States patent specification 2,304,- the light of a Xen0n Arc Fade Ometer (daylight spec 940. trum).

l3 The following table gives a clear showing of the light stability of a dyestuif formed on development by reaction of the oxidation product of N-diethyl-p-phenylenediamine formed thereby with a color coupler according tothe 14 substituted with a bivalent radical linked to a sulphonic acid-substituted phenyl group, said bivalent radical being a vmember of the group consisting of a CONH group, a SO NH group, and a -NHOONH- group.

present invention and known color couplersrfor yellow. 3. A photographic multi-layer color material contain- Maximum Maximum density density after 16 Percent Formula of the color coupler at the hours of decrease beginning exposing in max. of the inXenondensity test Arc-Fade- Ometer OCwHaa Na03S COCH2CONH 1. 1.10 8. 5

SOaNa 1a aa mmsUooomoomt 1.20 1. 03 14 l SOzNHUSOaNa HaaCmO CO CHiCONH 803E 1. 20 0. 99 18 (color coupler for yellow according to British patent specification 808,276) HmCmCONHUOO CHzCONHUCOOH 1. 20 0. 84 so (color coupler for yellow according to British patent specification 783,887)

In connection with the structure of the color couplers ing three silver halide emulsion layers optically diiferentaccording to the present invention, it is still to be noted that where the term sulfonic acid group or sulfonic acid substituent is used, the acid form as well as the salt form of this group or substituent is meant and the 1 salt form preferably contains as cation and alkali metal cation, ammonium group or amine salt group.

We claim:

1. A photographic material comprising a silver halide emulsion layer and a color coupler for yellow which is a benzoylacetanilide coupler wherein the benzoyl part of the color coupler is directly substituted with at least one sulphonic acid group or substituted with a bivalent radical linked to a sulphonic acid-substituted'phenyl group, and wherein the anilide part of the color coupler is directyl substituted with at least one sulphonic acid group' or substituted with a bivalent radical linked to a sulphonic acidsubstituted phenyl group, said bivalent radical being a member of the group consisting of a CONH- group, a -SO NH- group, and a -NHCONH- group.

2. A photographic multi-layer color material containing in a non-migratory form in one of the light-sensitive silver halide emulsion layers or in a non-light sensitive water permeable colloidal layer adjacent to a light-sensitive silver halide emulsion layer, a color coupler for yellow which is a benzoylacetanilide coupler wherein the benzoyl part of the color coupler is directly substituted with at least one sulphonic acid group or substituted with a bivalent radical linked to a sulphonic acid-substituted phenyl group, and wherein the anilide part of the color coupler is directly substituted with at least one sulphonic acid group or ly sensitive including a layer selected from the group consisting of a blue sensitive silver halide emulsion layer and a non-light sensitive water permeable colloidal layer adjacent thereto, at least one of said layers containing a color coupler for yellow which is a benzoylacetanilide coupler wherein the benzoyl part of the color coupler is directly substituted with at least one sulphonic acid group or substituted with a bivalent radical linked to a sulphonic acid-substituted phenyl group, and wherein the anilide part of the color coupler is directly substituted with at least one sulphonic acid group or substituted with a bivalent radical linked to a sulphonic acid-substituted phenyl group, said bivalent radical being a member of the group consisting of a CONH group, a AO NH group, and a -NHOONH-- group.

4. A photographic material comprising a silver halide emulsion layer and a color coupler for yellow having the general formula:

R1 R3 CD-co-om-o Q-NHQ R5 4 wherein R is a member selected from the group consisting of a sulfonic acid group and a salt thereof;

R is a member selected from the group consisting of a hydrogen atom and a sulfonic acid group, a salt form thereof, a halogen atom, and an organic group concontaining an acyclic aliphatic radical With 5 to 20 carbon atoms in straight line making the molecule non-migratory; and R and R together represent the necessary atoms for forming a sulfo-substitute-d aromatic system. 5. A photographic material comprising a silver halide emulsion layer and a color coupler for yellow having the general formula:

wherein R is a member selected from the group consisting of a hydrogen atom and a sulfonic acid group, a salt form thereof, a halogen atom, and an organic group containing an acyclic aliphatic radical with 5 to 20 carbon atoms in straight line making the molecule non-migratory;

R is a member selected from the group consisting of a sulfonic acid group and asalt form thereof;

R is a member selected from the group consisting of a hydrogen atom, and a sulfonic acid group, a salt form thereof, a halogen atom, and an organic group containing an acyclic aliphatic radical with 5 to 20 carbon atoms in straight line making the molecule non-migratory; r

R and R together represent the necessary atoms for forming a sulfo-substituted aromatic system;

Y is a member selected from the group consisting of CONH, -SO =NH- and -NHCONH-; and

R' is a sulfonated aromatic radical.

6. A photographic material comprising a silver halide emulsion layer and a color coupler for yellow having 7 the general formula:

16 form thereof, a halogenfatom, and anorganic group containing an acyclic aliphatic radical with 5 to 20 carbon atoms in straight line making the molecule non-migratory;

Y is a member selected from the group consisting of a -CONH- group or a SO NH- group; and R", is a sulfonated aromatic radical. g I 7. A photographic material comprising a silverhalide emulsion layer and a color coupler for yellow having the general formula:

wherein R is a member selected from the group consisting of a hydrogen atom and a sulfonic acid group, a salt form thereof, a halogen atom, and an organic group containing an acyclic aliphatic radical with 5 to 20 carbon atoms in straight line making the molecule non-migratory;

R is a member selected from the group consisting of a hydrogen atom, and a sulfonic acid group, a salt form thereof, a halogen atom, and an organic group containing an acyclic aliphatic radical with 5 to 20 carbon atoms in straight line making the molecule non-migratory;

Y is a member selected from the group consisting of w -CONH-, SO' NH- and -NHCONH-;

R is a sulfonated aromatic radical,

Y is a member selected from the group consisting of a CONH group or a SO NH- group; and

R" is a sulfonated aromatic radical.

8. The photographic material of claim 1 wherein the color coupler is ,SOaNa References Cited UNITED STATES PATENTS 3,112,198 11/1963 Klinger 96-56.6 2,895,825 7/ 1959 Pelz et a1. 96-566 2,950,314 8/1960 De Cat et al 96-566 3,056,674 10/ 1962 Hoflistadt et al. 96-100 2,662,913 12/ 1953 Eberhart et al. 260-507 2,836,620 5/ 1958 Bersworth et a1 260-507 2,933,391 4/ 1960 Feniak et al. 96-100 2,983,608 5/1961 Beavers 96-100 OTHER REFERENCES Glakfides, Photographic Chemistry, vol. 2, page 606, Fountain Press, London (1960).

TRAVIS BROWN, Primary Examiner. 

3. A PHOTOGRAPHIC MULTI-LAYER COLOR MATERIAL CONTAINING THREE SILVER HALIDE EMULSION LAYERS OPTICALLY DIFFERENTLY SENSITIVE INCLUDING A LAYER SELECTED FROM THE GROUP CONSISTING OF A BLUE SENSITIVE SILVER HALIDE EMULSION LAYER AND A NON-LIGHT SENSITIVE WATER PERMEABLE COLLOIDAL LAYER ADJACENT THERETO, AT LEAST ONE OF SAID LAYERS CONTAINING A COLOR COUPLER FOR YELLOW WHICH IS A BENZOYULACETANILIDE COUPLER WHEREIN THE BENZOYL PART OF THE COLOR COUPLER IS DIRECTLY SUBSTITUTED WITH AT LEAST ONE SULPHONIC ACID GROUP OR SUBSTITUTED WITH AVIVALENT RADICAL LINKED TO A SULPHONIC ACID-SUBSTITUTED PHENYL GROUP, AND WHEREIN THE ANILIDE PART OF THE COLOR COUPLER IS DIRECTLYU SUBSTITUTED WITH AT LEAST ONE SULPHONIC ACID GROUP OR SUBSTITUTED WITH A BIVALENT RADICAL LINKED TO A SULPHONIC ACID-SUBSTITUTED PHENYL GROUP, SAID BIVALENT RADICAL BEING A MEMBER OF THE GROUP CONSISTING OF A -CONH- GROUP, A -SO2NH- GROUP, AND A -NHCONH- GROUP. 